Decomposition of SF6 in an RF Plasma Environment

Abstract

Sulfur hexafluoride (SF₆)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF₆. The decomposition fraction of SF₆ [η_SF6 (C_in–C_out)/C_in x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O₂/SF₆ ratio in an SiO₂ reactor. The species detected in both SF₆/Ar and SF₆/O₂/Ar RF plasmas were SiF₄, SO₂, F₂, SO₂F₂, SOF₂, SOF₄, S₂F₁₀, S₂OF₁₀, S₂O₂F₁₀, and SF₄. The results revealed that at 40 W, η_SF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF₄, SO₂, and F₂ with or without the addition of oxygen. Sulfur oxyfluorides such as SO₂F₂, SOF₂, SOF₄, S₂OF₁₀, and S₂O₂F₁₀ were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF₆-containing exhaust gases.     

Total toxicity equivalents emissions of SF6, CHF3, and CCl2F2 decomposed in a RF plasma environment

Sulfur hexafluorine compound (SF6), trifluoromethane (CHF3) and diclorodifluoromethane (CCl2F2) are extensively used in the semiconductor industry. They are global warming gases. Most studies have addressed the effective decomposition of fluorine compounds, rather than the toxicity of decomposed by-products. Hence, the concepts of toxicity equivalents (TEQs) were applied in this work. The results indicated that HF and SiF4 were the two greatest contributors of TEQ to the SF6/H2/Ar plasma system, while F2 and SiF4 were the two greatest contributors to the SF6/O2/Ar system. Additionally, SiF4 and HF were the two greatest contributors of TEQ to both the CHF3/H2/Ar and CHF3/O2/Ar plasma systems. HF and HCl were the two greatest contributors of TEQ to the CCl2F2/H2/Ar plasma system, and Cl2 and COCl2 were the two greatest contributors to the CCl2F2/O2/Ar system. HCl and HF can be recovered using wet scrubbing, which reduces the toxicity of these emission gases. Consequently, the hydrogen-based plasma system was a better alternative for treating gases that contained SF6, CHF3 and CCl2F2 from the TEQs point of view.     

Predicting the contents of BTEX and MTBE for the three types of tollbooth at a highway toll station via the direct and indirect approaches

This study was set out to assess the contents of five volatile organic compounds (VOCs), including BTEX (the acronym for benzene, toluene, ethylbenzene, and xylene) and methyl tertiary-butyl ether (MTBE), in three types of tollbooth (including the car lane/ticket-collecting, car lane/cash-collecting, and bus/truck lane tollbooths) at a highway toll station via the direct and indirect approaches. For the direct approach, VOC samples were collected from the breathing zone of booth attendants at all selected tollbooths during the three workshifts. For samples collected during the dayshift, we found VOC contents of BTEX and MTBE in both the car lane/ticket-collecting (=6.23, 21.93, 3.24, 8.56, and 5.63 ppb, respectively) and car lane/cash-collecting tollbooths (=5.98, 21.71, 3.25, 8.59, and 6.04 ppb, respectively) were quite comparable, but both were significantly higher than that in the bus/truck lane tollbooth (=3.13, 13.91, 2.05, 4.52, and 2.70 ppb, respectively). The same pattern can also be found for the other two workshifts. For the indirect approach, we conducted multivariate regression analyses to predict VOC contents for any given type of tollbooth by using the four independent variables of the vehicle flowrate, wind speed, relative humidity, and air temperature. We found that, except the vehicle flowrate, the other three factors did not have a significant effect on VOC contents in the three types of tollbooth. In addition, the magnitudes of the effect of the vehicle flowrate on VOC contents for the three types of tollbooth were: car lane/cash-collecting>bus/truck lane>car lane/ticket-collecting. All regression results yielded R²-values in the range of 0.41−0.74 indicating that the developed indirect approach was able to predict VOC contents for three types of tollbooth.     

Fate of polycyclic aromatic hydrocarbons during vitrification of incinerator ash in a coke bed furnace

Fate of polycyclic aromatic hydrocarbons (PAHs) during the vitrification of fly ash and bottom ash from the municipal waste incinerator in a coke bed furnace was investigated. In this system, both coke and lime were added to enhance the melting reaction. The major PAH sources in this system were ash and coke, which respectively contributed 97% and 3% of PAHs in the input-mass. During vitrification process, low molecular PAHs (LM-PAH, 2-3-ring), median molecular PAHs (MM-PAH, 4-ring) and high molecular PAHs (HM-PAH, 5-7-ring) mass respectively accounted for >99%, >99% and 84% of the output-mass emitted as the stack flue gas; while those discharged from the slag were <1%, <1% and 16%, respectively. The O/I (output-mass/input-mass) ratio of LM-, MM- and HM-PAHs were 0.063, 0.002 and <0.001, respectively. The high distribution in flue gas and O/I ratio of LM-PAHs is reasonable since they are more easily evaporated, hence difficult to be removed by air pollution control devices. On the contrary, the HM-PAHs, having lower vapor pressure, primarily stays mainly in slag. Based on the 21 total PAH content in feeding ash and slag, the reduction efficiency of the coke bed furnace was >99.9%. To minimize the risk of secondary pollution, the efficiency of coke bed furnace should be improved to reduce the PAH emission into ambient air.     

A pilot study for determining the optimal operation condition for simultaneously controlling the emissions of PCDD/Fs and PAHs from the iron ore sintering process

In this study, the cost-benefit analysis technique was developed and incorporated into the Taguchi experimental design to determine the optimal operation combination for the purpose of providing a technique solution for controlling both emissions of PCDD/Fs and PAHs, and increasing both the sinter productivity (SP) and sinter strength (SS) simultaneously. Four operating parameters, including the water content, suction pressure, bed height, and type of hearth layer, were selected and all experimental campaigns were conducted on a pilot-scale sinter pot to simulate various sintering operating conditions of a real-scale sinter plant. The resultant optimal combination could reduce the total carcinogenic emissions arising from both emissions of PCDD/Fs and PAHs by 49.8%, and increase the sinter benefit associated with the increase in both SP and SS by 10.1%, as in comparison with the operation condition currently used in the real plant. The ANOVA results indicate that the suction pressure was the most dominant parameter in determining the optimal operation combination. The above result was theoretically plausible since the higher suction pressure provided more oxygen contents leading to the decrease in both PCDD/F and PAH emissions. But it should be noted that the results obtained from the present study were based on pilot scale experiments, conducting confirmation tests in a real scale plant are still necessary in the future.     

Effect of SiO2 on immobilization of metals and encapsulation of a glass network in slag

The final disposal of ash from an incinerator is of special concern because of the possibility of its releasing toxic substances. Melting/vitrification has been regarded as a prospective technology of ash treatment. The object of this investigation was to evaluate the effect of silica (SiO2) addition on the immobilization of hazardous metals and the encapsulation of a glass network during the vitrification process. Four specimens with SiO2/fly ash mixing ratios of 0, 0.1, 0.2, and 0.3, respectively, were tested. The mobility of metals in slag was then estimated by a sequential extraction procedure. X-ray diffraction analysis indicates that SiO2 leads to the polymerization of silicates. The encapsulation of aluminum, calcium, and magnesium would not be observed unless adequate amount of SiO2 was added. It was also found that SiO2 addition enhances the formation of a compact and interconnected glass network structure and, thus, contributes to the chemical stability of metals in slag. After vitrification, the mobility of cadmium, copper, iron, chromium, nickel, lead, and zinc was significantly reduced. However, there is no significant correlation between the immobilization of these metals and the addition of SiO2.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from stack flue gases of sinter plants

This study investigated four sinter plants, classified into two categories--with selective catalytic reduction (SCR) (S1, S2 and S3) and without SCR (S4) as its air pollution control device. Polychlorinated dibenzofurans (PCDFs) are dominant in the stack flue gases of sinter plants with and without SCR. The polychlorinated dibenzofurans/polychlorinated dibenzo-p-dioxins (PCDFs/PCDDs) ratio exceeds 1 extremely. The degree of chlorination of the sinter plant without SCR is towards hepta and hexa congeners while that of the sinter plant with SCR is towards penta and hexa congeners. PCDD/Fs are indeed decomposed (75.5% and 69% on ng and ng TEQ bases, respectively) and not only reduced in degree of chlorination. The overall concentration in the stack flue gas of sinter plants with SCR (7.97-14.1 ng/Nm(3); 0.995-2.06 ng TEQ/Nm(3)) is lower than that of the sinter plant without SCR (28.9 ng/Nm(3); 3.10 ng TEQ/Nm(3)). In Taiwan, based on the emission factors of 0.970 microg TEQ/ton-feedstock (sinter plants with SCR) and 3.13 microg TEQ/ton-feedstock (sinter plant without SCR), the annual PCDD/F emission of 44.7 g TEQ/year from sinter plants is 60 and 121 times higher than those from municipal solid waste incinerators (0.750 g TEQ/year) and MWIs (0.369 g TEQ/year). These results show that sinter plants have become the dominating PCDD/F emission source since tighter emission limits have been applied to incinerators.     

An integrated approach for identification of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) pollutant sources based on human blood contents

Background, aim, and scope  

This study developed an integrated approach to identify pollutant sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of workers based on their blood contents.     

Exposure and health-risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) for sinter plant workers

This study was set out to assess polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) exposures and health-risk impact posed on sinter plant workers. One sinter plant located in southern Taiwan was selected and their workers were divided into four exposure groups based on their work tasks, including raw material charging workers, sintering grate workers, shredding workers, and others. Results show that their mean total PCDD/F and the corresponding total I-TEQ exposure levels shared the same trend as: shredding workers>others>sintering grate workers>raw material charging workers. For all selected exposure groups, their PCDD/F exposures were dominated by the particle phase contents. Congener profiles of the gaseous+particle phase PCDD/Fs were found with more fractions of high chlorinated congeners than low chlorinated congeners. The lifetime average daily doses (LADDs) and their resultant excess cancer risks (ECRs) found for sinter plant workers were higher than those residents living at the residential area and rural area, but were lower than those living at the nearby of the selected sinter plant, urban area, industrial area. Considering ECRs of the sinter plant workers were still higher than 10(-6) suggesting the need for adopting proper control measurements for reducing workers' PCDD/F exposures, particularly for those sinter zone workers.     

Assessing inhalatory and dermal exposures and their resultant health-risks for workers exposed to polycyclic aromatic hydrocarbons (PAHs) contained in oil mists in a fastener manufacturing industry

This study first assessed workers' inhalatory and dermal exposures to polycyclic aromatic hydrocarbons (PAHs) contained in oil mists. Then, their resultant lung cancer and skin cancer risks were estimated. Finally, control strategies were initiated from the health-risk management aspect. All threading workers in a fastener manufacturing plant were included. 16 inhalatory and 88 dermal PAH exposure samples were collected. Results show that the inhalatory gas phase total PAH exposure level (8.60x10(4) ng/m(3)) was much higher than that of particle phase (2.30x10(3) ng/m(3)). Workers' mean inhalatory exposure level (8.83x10(4) ng/m(3)) was lower, but its corresponding 1-sided upper 95% confidence level (UCL(1,95%)=1.02x10(5) ng/m(3)) was higher than the time-weighted average permissible exposure level (PEL-TWA) regulated in Taiwan for PAHs (1.00x10(5) ng/m(3)). The mean whole body total PAHs dermal exposure levels was 5.44x10(6) ng/day and the top five exposed surface areas were lower arm, hand, upper arm, neck, and head/front. The estimated lifetime skin cancer risk (9.72x10(-3)) was lower than that of lung cancer risk (1.64x10(-2)), but both were higher than the significant risk level (10(-3)) defined by the US Supreme Court in 1980. The installation of a local exhaust ventilation system at the threading machine should be considered as the first priority measurement because both lung and skin cancer risks can be reduced simultaneously. If the personal protection equipment would be adopted in the future, both respiratory protection equipment and protective clothing should be used simultaneously.